CN103540349A - Inferior heavy oil and residual oil hydrotreating combined process for prolonging service life of catalyst - Google Patents
Inferior heavy oil and residual oil hydrotreating combined process for prolonging service life of catalyst Download PDFInfo
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- CN103540349A CN103540349A CN201210241248.8A CN201210241248A CN103540349A CN 103540349 A CN103540349 A CN 103540349A CN 201210241248 A CN201210241248 A CN 201210241248A CN 103540349 A CN103540349 A CN 103540349A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 59
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- 230000008569 process Effects 0.000 title claims abstract description 22
- 239000000295 fuel oil Substances 0.000 title claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 51
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 238000005516 engineering process Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 12
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- 239000002245 particle Substances 0.000 claims description 10
- 239000012263 liquid product Substances 0.000 claims description 9
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000007324 demetalation reaction Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
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- 230000008676 import Effects 0.000 claims description 4
- 238000009955 starching Methods 0.000 claims description 4
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- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- -1 VIB metals Chemical class 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
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- 238000012986 modification Methods 0.000 abstract description 4
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- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000002779 inactivation Effects 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
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- 230000007774 longterm Effects 0.000 description 4
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- 239000004480 active ingredient Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002010 green coke Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 230000009849 deactivation Effects 0.000 description 2
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- 238000001125 extrusion Methods 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 238000005470 impregnation Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
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- 229910001145 Ferrotungsten Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 238000005345 coagulation Methods 0.000 description 1
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- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
The invention relates to a poor heavy oil and residual oil hydrotreating combined process, wherein a heavy oil raw material is subjected to hydrogenation pretreatment in a slurry bed, after gas-liquid separation, a liquid-phase product is subjected to hydrogenation modification in a fixed bed, wherein the hydrogenation pretreatment part in the slurry bed comprises a slurry bed hydrogenation reactor and a slurry bed hydrogenation catalyst; the reactors used in the fixed bed hydro-upgrading part mainly comprise the following components in sequence: the method not only improves the hydrogenation and impurity removal capability of the catalyst, but also can prolong the life cycle of the catalyst, can treat residual oil with high metal content, high sulfur, high nitrogen and high asphaltene, and can effectively slow down the rising speed of the pressure drop of the reactor, thereby realizing the long-period operation of the device.
Description
Technical field
The inventive method can be used for field of hydrogenation, is particularly useful for high metal (Ni+V>=200 μ gg
-1), hydrofining and the hydrotreatment of heavy distillate, residual oil and the oil sands bitumen of high carbon residue (CCR>=20wt%), high asphalt content.The inventive method guaranteeing on the active basis of higher demetalization, desulfurization, denitrogenation and diasphaltene, is extending catalyst work-ing life, and improving device long-term operation performance provides an effective way.
Background technology
At present, along with the aggravation of crude oil in poor quality, heaviness trend, the increase of light-end products demand and the increasingly stringent of environmental regulation, the processing modification technology of residual oil has caused the extensive concern of countries in the world.The deep processing of poor residuum and upgrading, for rationally utilizing petroleum resources, improve quality product, improve yield of light oil, have important practical significance.
Residue Hydrotreating Technology is because liquid product yield is high, quality is good, both can meet to maximum the increase of market to light-end products demand, can produce again more clean petroleum products to meet increasingly strict environmental requirement, be the development trend place of residua upgrading technology.From type of reactor, divide, comprise fixed bed, ebullated bed, moving-bed and slurry state bed hydroprocessing Four types, fixed bed and moving-bed hydrogenation technique, to having relatively high expectations of raw material, be not suitable for processing heavy, inferior raw material; Boiling bed hydrogenation technology can be processed inferior raw material, but operational condition is harsh, and plant investment cost is higher; Slurry state bed hydroprocessing technology can be processed various inferior raw materials, has that adaptability to raw material is strong, technique simple, a flexible operation, transformation efficiency high, but not yet realizes industrialization because of problems such as reaction green coke and engineering amplifications.In a word, the core of residual hydrogenation upgrading is reasonably to control depth of conversion, and the macromole that bituminous matter etc. is easy to coagulation progressively transforms on the basis that colloidal dispersion is stable keeping, thereby avoids green coke to cause catalyst deactivation to shorten device running period.The success of residual hydrogenation upgrading need to be amplified basic chemistry understanding, the appropriate design of hydrogenation catalyst and the science of technological process of residual oil organically to combine and could realize.On industrial practice, in order to improve catalyzer work-ing life, prolong operating period, investigator has proposed multiple solution.
CN1322097C discloses a kind of replaceable reactor and method that can short-circuit reaction device hydrotreatment of heavy hydrocarbon fraction of adopting.First residual oil processed through a protective belt, and at protection section, catalyst regeneration or replacing can short circuit be guaranteed in protective belt; And then process through hydrodemetallation (HDM) and hydrogenating desulfurization, the reactor of at least one hydrodemetallation (HDM) section and/or hydrodesulfurizationsection section can short circuit, is beneficial to regeneration and the replacing of catalyzer.By protection and the replacing of catalyzer, guarantee that device can long-term operation, but need higher initial outlay.
CN1349554 discloses a kind of method of the up-flow reactor system hydrotreating heavy feedstocks with stratiform beds.The heavy feed stock polluting by the residual matter of upflow fixed bed reactor hydrotreatment metal, sulphur and carbon containing of the catalyzer of at least two different hydrogenation activities.But the method cycle of operation is short, be generally no more than 1 year.
CN1144860 discloses a kind of method of residual hydrocracking.First reactor in heavy residual hydrogenation reactive system is set up one or more opening for feeds, change original catalyzer grating simultaneously, when an anticatalyzer bed pressure drop designs 0.4-0.8 times of maximum pressure drop for device, use successively next opening for feed instead, original opening for feed can enter the mixture of turning oil or turning oil and stock oil simultaneously.This technique can effectively prevent bed pressure drop and extend the work-ing life of residual oil hydrocatalyst, and can increase the processing power of device.
CN00110714.3 discloses a kind of residual oil treatment process.Before heavy residual hydrogenation reactive system, adopt one section of absorption filter agent bed or one section of absorption filter agent bed and one section of adsorption filtration beds to use simultaneously, not only can farthest remove the suspended particle carrying in stock oil, but also can remove Iron sulfuret and the most of easily material of green coke that the iron naphthenate in crude oil generates, at utmost reduce the fouling of residual hydrogenation reactive system reactor, reduce the shutting down number of times that because of fouling cause of device in running period.
Residual oil density is large, and viscosity is high, and impurity is many, only relies on single processing means to be difficult to obtain desirable product and benefit.Fixed bed hydrogenation process costs is low, simple to operate, technology maturation, but can only the good raw material of handling properties; Slurry state bed hydroprocessing technology can be processed various inferior raw materials, there is the features such as adaptability to raw material is strong, flexible operation, consider the features of fixed bed and slurry state bed hydroprocessing, the present invention plans two kinds of techniques and combines, poor residuum is first through starching state bed hydroprocessing as pre-treatment, metal in raw material, sulphur, nitrogen, asphalt content are significantly reduced, and then process through fixed bed hydrogenation, further remove impurity wherein, avoid because raw material viscosity is large, metallic impurity or asphalt content higher, cause catalyzer rapid deactivation, shorten device running period.
Summary of the invention
The object of this invention is to provide a kind of inferior heavy oil, process for hydrogenating residual oil, by adopting unique hydrotreatment flow process, and select rightly effective hydrogenation catalyst, reach and both improve catalyst hydrogenation removing impurities mass-energy power, again the extension fixture cycle of operation.
A kind of inferior heavy oil, residual hydrocracking combination process, it is characterized in that heavy oil and/or residual oil raw material are first through the pre-treatment of slurry state bed hydroprocessing, after gas-liquid separation, liquid product is again through fixed bed hydrogenation upgrading, wherein, slurry state bed hydroprocessing preprocessing part comprises a slurry state bed hydroprocessing reactor and slurry state bed hydroprocessing catalyzer, fixed bed hydrogenation upgrading part is reactor used mainly to be comprised sequentially: two upflowing deferrization decalcification reactors, a upflowing demetalization reactor, a fixed bed desulphurization reactor, a fixed bed denitrification reactor, specific as follows: on the inlet line of two upflowing deferrization decalcification reactors and outlet line, to be all equipped with check valve, before outlet line check valve with after another upflowing deferrization decalcification Reactor inlet pipeline check valve, be connected with a pipeline, make material be able to import from the outlet of a upflowing deferrization decalcification reactor import of another upflowing deferrization decalcification reactor, on pipeline, be equipped with check valve, on the inlet line of upflowing demetalization reactor and outlet line, be all equipped with 3-way valve, other two ends in the 3-way valve of upflowing demetalization Reactor inlet pipeline, one end connects the outlet line of streaming demetalization reactor, the other end pipeline connects the 3-way valve on streaming demetalization reactor outlet pipeline, and this 3-way valve also has the source line of one end and fixed bed desulphurization reactor to join, first raw material forms suspension slurry with slurry state bed hydroprocessing catalyst mix, then enter slurry state bed hydroprocessing reactor and add hydrogen pretreatment, exported product is through gas-liquid separator, hydrogen-containing gas and liquid product are separated, liquid product is through upflowing deferrization decalcification reactor, the in-built hydrogen deferrization decalcification catalyzer of dosing of reactor, remove a part of iron, slurry state bed catalyst after calcium and slurry state bed hydroprocessing are processed, its resultant of reaction has two kinds of operation scheme: the one, directly enter upflowing demetalization reactor, under existing, catalyst for demetalation carries out hydrodemetallation (HDM) (Ni, V) reaction, its resultant of reaction is without separation again, directly enter fixed bed desulphurization reactor, under existing, desulfurization catalyst carries out hydrodesulfurization reaction, the 2nd, directly enter desulphurization reactor, under existing, desulfurization catalyst carries out hydrodesulfurization reaction, desulphurization reactor resultant of reaction, without separation, directly enters fixed bed denitrification reactor, under denitrification catalyst exists, carries out hydrodenitrification reaction.
In the present invention, the raw material such as residual oil, heavy oil is after slurry state bed hydroprocessing is processed, product is after separation, the liquid product that contains slurry state bed hydroprocessing catalyst particles enters upflowing deferrization decalcification reactor, after deferrization calcium catalyst is processed, slurry state bed catalyst particle can effectively be caught, thus the life cycle that extends fixed bed desulfurization catalyst.
Deferrization decalcification device operational process step can be as follows:
(1) in initial reaction stage, two deferrization decalcification reactors are used together, and heavy oil or residual oil raw material are introduced into one of them reactor (representing with A), then enter another reactor (representing with B) and carry out deferrization decalcification reaction.
(2) after reaction for some time, A reactor catalyst activity approaches the middle and later periods, at this moment can flow to by feed change, and the advanced B reactor of raw material enters A reactor again.
(3) in A reactor, deferrization decalcification catalyzer, in the inactivation stage, is closed A reactor feed valve, and with regeneration and/or replace the catalyzer of reactor with live catalyst.Now material only enters B reactor.
(4) A completes and changes after agent, the advanced B reactor of material, then enter to change the reactor A of agent.
(5) in B reactor, deferrization decalcification catalyzer, in the inactivation stage, is closed B reactor feed valve, and with regeneration and/or replace the catalyzer of reactor with live catalyst.Now material only enters A reactor.
(6) B reactor completes and changes after agent, continues repeating step (1)-step (5).
For demetalization reactor, in operational process, especially, in the active inactivation stage of catalyst for demetalation, material autoreactor out directly enters desulphurization reactor.Use the catalyst for demetalation of regenerating and/or replacing reactor with live catalyst simultaneously.Complete after catalyzer replacement, material autoreactor out enters demetalization reactor, desulphurization reactor and denitrification reactor more successively.
Method provided by the present invention can be processed high metal content, high-sulfur, high nitrogen, high bitum residual oil, and can effectively slow down the lift velocity of reactor pressure decrease, thus the long-term operation of implement device.
The logistics direction of up-flow reactor of the present invention is to flow through from bottom to top beds, slightly microdilatancy of the catalyzer in bed.After mink cell focus or residual oil raw material and hydrogen mix, from up-flow reactor bottom feed, make whole beds produce slight expansion, thereby slow down the rate of growth of the Pressure Drop of beds, the running period of extension fixture.Same ebullated bed, moving-bed and slurry state bed are compared, and up-flow reactor has the features such as low, simple to operate of investing.
Slurry state bed hydroprocessing catalyzer can form suspension slurry with stock oil, upflowing deferrization decalcification reactor charge hydrogenation deferrization decalcification catalyzer, demetalization reactor charge Hydrodemetalation catalyst, desulphurization reactor filling Hydrobon catalyst, denitrification reactor filling hydrodenitrogenation catalyst.
In the present invention, hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, from left to right, preferably: catalyzer aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
In the present invention, in 4 classification fixed-bed reactor of fixed bed hydrogenation upgrading part, can load respectively one or more catalyzer, preferably, along logistics direction, aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
Slurry state bed hydroprocessing catalyzer preferably be take composite catalyst that carbonaceous particle and part molybdenum nickel metal oxide form as main, can be also the mineral substance that is rich in the metal active constituents such as nickel, molybdenum, vanadium, iron.Activated-carbon catalyst, for the heavy hydrocarbons in residual oil and the selective adsorption of bituminous matter, has the good burnt ability that presses down; Meanwhile, activated-carbon catalyst has very high reactivity for the metallic impurity such as nickel vanadium that remove in bituminous matter; Stability Analysis of Structures under active carbon high-temp, acid and alkali-resistance, active ingredient is easy to sulfuration completely, than traditional aluminum oxide and silicon oxide catalyst, has higher HDS/HDN activity; Surface chemical property can regulate modification, is easy to reclaim precious metal wherein.
US4831003 and US5051389 have proposed a kind of precursor by molybdenum or nickel isoreactivity metal component and have adopted the method for gas phase distillation deposition to load to the method on gac, and the standby catalyzer of this legal system can be used for the hydrotreatment of heavy oil and dilution stock oil.
US5358634, US5364524, US5374350 select a kind of mean pore size be the gac of 10-40nm as carrier, employing is sequentially flooded or co-impregnation load molybdenum cobalt isoreactivity component, this catalyzer has good HDM effect in fixed bed, moving-bed.
It is carrier that US5389241, US5500401 be take 20-40 object gac, and employing order pickling process is prepared the catalyzer of processing for heavy oil HDN, and the alumina load type catalyst activity that its specific activity is traditional is high.
The metal components such as US5466363 be take gac as carrier, nickel-loaded cobalt molybdenum ferrotungsten are for fixed bed or moving-bed hydrotreatment, and a part of gasification of the catalyzer of inactivation, produces synthetic gas synthetic for Fischer-Tropsch, and a part can be used for making steel in addition.
US5676822 be take gac as carrier, adopts the metals such as co-impregnation zinc supported or nickel ferro-cobalt, for removing the impurity such as the aromatic hydrocarbons of petroleum naphtha or intermediate oil and sulphur nitrogen.
EP1537912A1 discloses a kind of activated-carbon catalyst preparation method for fixed bed/moving-bed/boiling bed heavy oil hydrogenation.Carrier active carbon is through water vapour modification, and mean pore size, between 20-200nm, forms catalyzer after dip loading iron isoreactivity component, can effectively suppress the generation of coking in reaction process.
Recommend adoption equi-volume impregnating supported active metal component of the present invention, prepares the slurry state bed hydroprocessing catalyzer of high reactivity, anti-coking.The specific surface area particularly adopting is 400～2000m
2/ g, is preferably 800～1000m
2the carbonaceous particle of/g is carrier, and active metal oxide charge capacity is preferably 300～1500 μ g/g, is preferably 500～1000 μ g/g, and active metal oxide is taken from group VIB metal and/or VIII family metal.
In order to improve the capturing ability of impurity, dust and particle, the hydrogenation deferrization decalcification catalyzer using in the present invention is preferably honeycomb shape, and order number is between 50～400.Generally take porous inorganic oxide as aluminum oxide be carrier, group VIB metal (as W or/and Mo) and/or VIII family metal (as Co or/and Ni) oxide compound is active ingredient, the composition of catalyzer is preferably:
1) with Al
2o
3or contain K
2o, MgO, SiO
2, TiO
2, ZrO
2al
2o
3as carrier;
2) pore volume is 0.1～3.0ml/g, is preferably 0.3～1.3ml/g;
3) specific surface is 200～1000m
2/ g, is preferably 400～800m
2/ g;
4) porosity is 30%～70%, is preferably 50-60%;
5) catalyzer, in corresponding burning amount (as follows), contains 1.0～10.0%, is preferably 5.0～8.0% group VIB metal (as MoO
3and/or WO
3), and/or 0.5～3.0%, be preferably 1.0～2.0% VIII family metal (as CoO and/or NiO).
The Hydrodemetalation catalyst using in the present invention, Hydrobon catalyst and/or hydrodenitrogenation catalyst, preferably take porous inorganic oxide as aluminum oxide be carrier, group VIB metal (as W or/and Mo) and/or VIII family metal (as Co or/and Ni) oxide compound is active ingredient, and the composition of catalyzer is preferably:
1) with Al
2o
3or contain K
2o, MgO, SiO
2, TiO
2, ZrO
2al
2o
3as carrier;
2) pore volume is 0.1～3.0ml/g, is preferably 0.3～1.3ml/g;
3) specific surface is 20～400m
2/ g, is preferably 100～240m
2/ g;
4) catalyzer, in corresponding burning amount (as follows), contains 1.0～20.0%, is preferably 3.0～16% group VIB metal (as MoO
3and/or WO
3), and/or 0.5～8.0%, be preferably 1.0～5.5% VIII family metal (as CoO and/or NiO).
It should be noted that, the catalyzer relating in the present invention can adopt ordinary method of the prior art to prepare.
The catalyzer using in the present invention, its carrier can be to drip ball forming, spin granulation, extrusion molding, compression molding etc., take a ball forming and extrusion molding as best.Catalyst shape can be honeycombed, spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape.With honeycombed, spherical and Herba Galii Bungei, be shaped as best.
Heavy oil of the present invention, residual hydrocracking technique, can adopt the hydroprocessing technique condition of any applicable this area, general processing condition are as follows: hydrogen pressure 5.0MPa～20.0MPa, be preferably 8.0MPa～18.0MPa, and that best is 10.0MPa～16.0MPa; 300 ℃～450 ℃ of temperature, are preferably 360 ℃～440 ℃, and best is 360 ℃～430 ℃; Volume space velocity 0.2h during liquid
-1～3h
-1, be preferably 0.2h
-1～2h
-1, that best is 0.2h
-1～1h
-1; Hydrogen to oil volume ratio 300～2000, is preferably 400～1500, and best is 500～1000.
Slurry state bed hydroprocessing pretreatment technology condition is as follows: hydrogen pressure 8.0MPa～20.0MPa, be preferably 8.0MPa～18.0MPa, and that best is 10.0MPa～16.0MPa; 350 ℃～450 ℃ of temperature, are preferably 380 ℃～440 ℃, and best is 400 ° of C～420 ℃; Volume space velocity 0.2h during liquid
-1～3h
-1, be preferably 0.2h
-1～2h
-1, that best is 0.5h
-1～1h
-1; Hydrogen to oil volume ratio 300～2000, is preferably 400～1500, and best is 500～1000.In stock oil, 0.5wt%～5wt% that slurry state bed hydroprocessing catalyzer add-on is stock oil, catalyzer can adopt prior art preparation.
Transformation efficiency calculates take raw material as benchmark, while being residual oil as raw material, i.e. and transformation efficiency=(1-is unconverted residual oil/charging residual oil) * 100%.
Because deferrization decalcification reactor, demetalization reactor in the present invention have been selected up-flow reactor, the logistics direction of up-flow reactor is to flow from bottom to top, and in reactor, liquid phase is continuous, slightly microdilatancy of the catalyzer in bed.Same ebullated bed, moving-bed and slurry state bed are compared, and up-flow reactor has the features such as low, simple to operate of investing.Mink cell focus of the present invention, residual oil raw material first with slurry state bed hydroprocessing catalyst mix, form suspension slurry, after preheating, enter slurry state bed hydroprocessing reactor and carry out hydrocracking, exported product is through gas-liquid separator, hydrogen-containing gas and liquid product are separated, liquid product is from the bottom feed of the upflowing deferrization decalcification reactor of fixed bed hydrogenation treatment unit, make whole beds produce slight expansion, thereby slow down the rate of growth of the Pressure Drop of beds, when the technical process adopting can be avoided deferrization decalcifying agent and demetalization inactivation, sweetening agent and denitrfying agent activity also have the situation that sizable potentiality can not effectively be brought into play to occur.Be recommended in deferrization decalcification reactor, demetalization reactor, desulphurization reactor and denitrification reactor simultaneously and select special catalyst, be particularly suitable for processing high-sulfur, high metal content, high bitum residual oil, the long-term operation of implement device.
Accompanying drawing explanation
Fig. 1 is application a kind of inferior heavy oil of the present invention or residual hydrocracking process flow diagram.Method the present invention being improved below in conjunction with accompanying drawing is further described, but does not thereby limit the invention.
Inferior heavy oil or residual oil raw material first with slurry state bed hydroprocessing catalyst mix, form suspension slurry, after preheating, enter slurry state bed hydroprocessing reactor and carry out hydrocracking, then effluent enters the up-flow reactor R-1A of fixed bed hydrogenation treatment unit and/or the bottom of R-1B, contact with up-flow reactor catalyzer and carry out deferrization decalcification reaction, its resultant of reaction has two operation scheme: the one, without separation, directly enter the bottom of up-flow reactor R-2, under existing, catalyzer carries out hydrodemetallation (HDM) (Ni, V) reaction, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor R-3, under existing, catalyzer carries out hydrodesulfurization reaction, the 2nd, directly enter desulphurization reactor, under existing, catalyzer carries out hydrodesulfurization reaction.Its desulphurization reactor resultant of reaction, without separation, directly enters fixed bed denitrification reactor R-4.
Deferrization decalcification device operational process step is as follows:
(1) in initial reaction stage, R-1A is used together with R-1B reactor, and heavy oil or residual oil raw material are introduced into R-1A, then enters R-1B and carry out deferrization decalcification reaction.
(2) after reaction for some time, R-1A reactor catalyst activity approaches the middle and later periods, at this moment can flow to by feed change, and the advanced R-1B reactor of raw material enters R-1A reactor again.
(3) in R-1A reactor, deferrization decalcification catalyzer, in the inactivation stage, is closed R-1A reactor feed valve, and with regeneration and/or replace the catalyzer of reactor with live catalyst.Now material only enters R-1B reactor.
(4) R-1A completes and changes after agent, the advanced R-1B reactor of material, then enter to change the reactor R-1A of agent.
(5) in R-1B reactor, deferrization decalcification catalyzer, in the inactivation stage, is closed R-1B reactor feed valve, and with regeneration and/or replace the catalyzer of reactor with live catalyst.Now material only enters R-1A reactor.
(6) continue repeating step (1)-step (5).
For demetalization reactor R-2, in operational process, especially, in catalyst for demetalation active latter stage, material out can directly enter desulphurization reactor R-3 from deferrization decalcification reactor.And with regeneration and/or replace the catalyst for demetalation of reactor with live catalyst.Complete after catalyzer replacement, material out enters demetalization reactor R-2, desulphurization reactor R-3 and denitrification reactor R-4 more successively from deferrization decalcification reactor.
Embodiment
Embodiment is all used the hydroprocessing technique of the inferior heavy oil shown in Fig. 1 or residual oil.
Embodiment 1
Take raw material A as raw material (character is in Table 1), under combination process flow process, process 2000h.Slurry state bed hydroprocessing pretreatment technology condition is as follows: hydrogen pressure 18.0MPa; 430 ℃ of temperature; Volume space velocity 0.6h during liquid
-1; Hydrogen to oil volume ratio 1000; Slurry state bed catalyst is carbonaceous particle and molybdenum oxide composite catalyst, and add-on is 5%, and slurry state bed hydroprocessing catalyzer prepares according to method in embodiment in CN102049252A 2.The processing condition that fixed bed hydrogenation is processed are as follows: hydrogen pressure 18.0MPa; 390 ℃ of temperature; Volume space velocity 0.3h during liquid
-1; Hydrogen to oil volume ratio 1000.Each reactor charge catalyzer is followed successively by hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst.The honeycomb shape deferrization decalcifying agent BN-01A(80 order that hydrogenation deferrization decalcification catalyzer adopts Jiangxi Ying Taokangshun Industrial Co., Ltd. to produce); In Hydrodemetalation catalyst, Hydrobon catalyst employing CN101928593A, in embodiment 1, method makes; Hydrodenitrogenation catalyst, in employing CN101928593A, in embodiment 2, method makes.Hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrodenitrification agent, additional proportion is respectively 18%, 20%, 30%, 32%.
Take raw material B as raw material (character is in Table 1), through combination process, process 2000h.Slurry state bed hydroprocessing pretreatment technology condition is as follows: hydrogen pressure 12.0MPa; 390 ℃ of temperature; Volume space velocity 0.2h during liquid
-1; Hydrogen to oil volume ratio 800; Slurry state bed hydroprocessing catalyzer, with embodiment 1, is carbonaceous particle and nickel oxide composite catalyst, and add-on is 0.5%.The processing condition that fixed bed hydrogenation is processed are as follows: hydrogen pressure 12.0MPa; 385 ℃ of temperature; Volume space velocity 0.25h during liquid
-1; Hydrogen to oil volume ratio 800.Each reactor charge catalyzer is followed successively by hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst.Catalyzer and additional proportion are with embodiment 1.
Comparative example 1
Take raw material A as raw material (character is in Table 1), same with embodiment 1, only through fixed bed hydrogenation, process 2000h.The processing condition that fixed bed hydrogenation is processed are as follows: hydrogen pressure 18.0MPa; 390 ℃ of temperature; Volume space velocity 0.3h during liquid
-1; Hydrogen to oil volume ratio 1000.Each reactor charge catalyzer is followed successively by hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst.Catalyzer and additional proportion are with embodiment 1.
Comparative example 2
Take raw material B as raw material (character is in Table 1), same with embodiment 2, only through slurry state bed hydroprocessing pretreatment technology 2000h.Slurry state bed hydroprocessing pretreatment technology condition is as follows: hydrogen pressure 12.0MPa; 385 ℃ of temperature; Volume space velocity 0.25h during liquid
-1; Hydrogen to oil volume ratio 800; Slurry state bed hydroprocessing catalyzer, with embodiment 1, is carbonaceous particle and nickel oxide composite catalyst, and add-on is 0.5%.
Table 1 is evaluated feedstock property and is formed
The main physico-chemical property of table 2 used catalyst of the present invention
2000 hours longevity test results of table 3
Claims (14)
1. an inferior heavy oil, residual hydrocracking combination process, it is characterized in that heavy oil and/or residual oil raw material are first through the pre-treatment of slurry state bed hydroprocessing, after gas-liquid separation, liquid product is again through fixed bed hydrogenation upgrading, wherein, slurry state bed hydroprocessing preprocessing part comprises a slurry state bed hydroprocessing reactor and slurry state bed hydroprocessing catalyzer, fixed bed hydrogenation upgrading part is reactor used mainly to be comprised sequentially: two upflowing deferrization decalcification reactors, a upflowing demetalization reactor, a fixed bed desulphurization reactor, a fixed bed denitrification reactor, specific as follows: on the inlet line of two upflowing deferrization decalcification reactors and outlet line, to be all equipped with check valve, before outlet line check valve with after another upflowing deferrization decalcification Reactor inlet pipeline check valve, be connected with a pipeline, make material be able to import from the outlet of a upflowing deferrization decalcification reactor import of another upflowing deferrization decalcification reactor, on pipeline, be equipped with check valve, on the inlet line of upflowing demetalization reactor and outlet line, be all equipped with 3-way valve, other two ends in the 3-way valve of upflowing demetalization Reactor inlet pipeline, one end connects the outlet line of streaming demetalization reactor, the other end pipeline connects the 3-way valve on streaming demetalization reactor outlet pipeline, and this 3-way valve also has the source line of one end and fixed bed desulphurization reactor to join, first raw material forms suspension slurry with slurry state bed hydroprocessing catalyst mix, then enter slurry state bed hydroprocessing reactor and add hydrogen pretreatment, product is after gas-liquid separation, liquid product is through upflowing deferrization decalcification reactor, the in-built hydrogen deferrization decalcification catalyzer of dosing of reactor, remove a part of iron, slurry state bed catalyst after calcium and slurry state bed hydroprocessing are processed, its resultant of reaction has two kinds of operation scheme: the one, without separation, directly enter upflowing demetalization reactor, under existing, catalyst for demetalation carries out hydrodemetallation (HDM) reaction, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor, under existing, desulfurization catalyst carries out hydrodesulfurization reaction, the 2nd, directly enter desulphurization reactor, under existing, desulfurization catalyst carries out hydrodesulfurization reaction, desulphurization reactor resultant of reaction, without separation, directly enters fixed bed denitrification reactor, under denitrification catalyst exists, carries out hydrodenitrification reaction.
2. technique according to claim 1, is characterized in that hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, and catalyzer aperture reduces gradually from left to right, and granularity reduces gradually, and porosity reduces gradually.
3. technique according to claim 1, is characterized in that reactor used middle one or more catalyzer that load respectively of fixed bed hydrogenation upgrading part, and along logistics direction, aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
4. technique according to claim 1, is characterized in that starching state bed hydroprocessing pretreatment technology condition and is: hydrogen pressure 8.0MPa～20.0MPa; 350 ℃～450 ℃ of temperature; Volume space velocity 0.2h during liquid
-1～3h
-1; Hydrogen to oil volume ratio 300～2000.
5. technique according to claim 1, is characterized in that starching state bed hydroprocessing catalyzer and adopts equi-volume impregnating supported active metal component to obtain, and carrier is that specific surface area is 400～2000m
2the carbonaceous particle of/g, in catalyzer, active metallic content is 300～1500 μ g/g; Catalyzer add-on accounts for the 0.5wt%～5wt% of stock oil.
6. technique according to claim 5, is characterized in that starching active metal oxide in state bed hydroprocessing catalyzer and takes from group VIB metal and/or VIII family metal, and content is 500～1000 μ g/g.
7. technique according to claim 1, is characterized in that fixed bed hydrogenation upgrading part processing condition are: hydrogen pressure 5.0MPa～20.0MPa; 300 ℃～450 ℃ of temperature; Volume space velocity 0.2h during liquid
-1～3h
-1; Hydrogen to oil volume ratio 300～2000.
8. technique according to claim 1 and 2, is characterized in that hydrogenation deferrization decalcification catalyzer is:
1) with Al
2o
3or contain K
2o, MgO, SiO
2, TiO
2, ZrO
2al
2o
3as carrier;
2) pore volume is 0.1～3.0ml/g;
3) specific surface is 50～200m
2/ g;
4) porosity is 40%～75%;
5) catalyzer, in corresponding burning amount, contains 1.0～10.0% group VIB metals and/or 0.5～3.0% VIII family metal.
9. technique according to claim 8, is characterized in that hydrogenation deferrization decalcification catalyzer pore volume is 0.3～1.3ml/g, and specific surface is 80～150m
2/ g.
10. technique according to claim 8, is characterized in that hydrogenation deferrization decalcification catalyzer contains 1.0～10.0% MoO
3, WO
3in one or both and/or 0.5～3.0% CoO, one or both in NiO.
11. techniques according to claim 1 and 2, is characterized in that Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst consist of:
1) with Al
2o
3or contain K
2o, MgO, SiO
2, TiO
2, ZrO
2al
2o
3as carrier;
2) pore volume is 0.1～3.0ml/g;
3) specific surface is 20～400m
2/ g;
4) catalyzer is in corresponding burning amount, contains 1.0～20.0% group VIB metal and/or 0.5～8.0% VIII family metal.
12. techniques according to claim 11, is characterized in that Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst pore volume are 0.3～1.3ml/g, and specific surface is 100～240m
2/ g.
13. techniques according to claim 11, is characterized in that Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst contain 1.0～20.0% MoO
3, WO
3in one or both, and/or 0.5～8.0% CoO, one or both in NiO.
14. techniques according to claim 11, is characterized in that Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst contain 3.0～16% MoO
3, WO
3in one or both, and/or 1.0～5.5% CoO, one or both in NiO.
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